DK167025B - IONIC COPOLYMER WITH GOOD LOW TEMPERATURE CHARACTERISTICS, ITS MANUFACTURING AND USE - Google Patents

IONIC COPOLYMER WITH GOOD LOW TEMPERATURE CHARACTERISTICS, ITS MANUFACTURING AND USE Download PDF

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DK167025B
DK167025B DK600283A DK600283A DK167025B DK 167025 B DK167025 B DK 167025B DK 600283 A DK600283 A DK 600283A DK 600283 A DK600283 A DK 600283A DK 167025 B DK167025 B DK 167025B
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Robert Joseph Statz
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Du Pont
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Description

iin

DK 167025 BDK 167025 B

Den foreliggende opfindelse angår ioniske copolymere, især ioniske copolymere med en lav grad af kædeforgrening, en fremgangsmåde til deres fremstilling og deres anvendelse.The present invention relates to ionic copolymers, in particular ionic copolymers having a low degree of chain branching, a process for their preparation and their use.

Copolymere af ethylen og acryl- eller methacryl-5 syrer, der er delvis neutraliserede med metalioner, såsom natrium- eller zinkioner, (ethylenionomere) er velkendte og er seje formstof harpikser med en kombination af gode trækstyrkeegenskaber og en fremragende slidbestandighed.Copolymers of ethylene and acrylic or methacrylic acids partially neutralized with metal ions such as sodium or zinc ions (ethylene ionomers) are well known and are tough resin resins with a combination of good tensile properties and excellent abrasion resistance.

Deres ulempe er, at de ved lave temperaturer bliver alt 10 for stive.Their disadvantage is that at low temperatures, they become overly stiff.

I US-patentskrift nr. 3.264.272 beskrives ethy-len/methacrylsyre/acrylsyre-ester-copolymere og ionomere fremstillet ud fra disse materialer. Der beskrives polymerisation ved høje tryk på 50-3.000 atm. og forhøjede 15 temperaturer på 150-300°C i nærværelse af en fri-radikal--polymerisationsinitiator.U.S. Patent No. 3,264,272 describes the ethylene / methacrylic acid / acrylic acid ester copolymers and ionomers prepared from these materials. Polymerization is described at high pressures of 50-3,000 atm. and elevated temperatures of 150-300 ° C in the presence of a free radical polymerization initiator.

I DE-offentliggørelsesskrift nr. 2.341.462 beskrives ethylen/acrylat/syre-copolymere og -.'ionomere og reaktortemperaturer på 150-300"C. Eksemplerne i skriftet 20 gennemføres imidlertid kun ved polymerisationstemperaturer på 215°C eller mere.In DE Publication No. 2,341,462, ethylene / acrylate / acid copolymers and ionomers and reactor temperatures of 150-300 ° C are described. However, the examples in the specification 20 are carried out only at polymerization temperatures of 215 ° C or more.

I skriftet nævnes en lang række acrylater, f.eks. isobutylacrylat, samt methacrylater, maleater og fumarater. Endvidere nævnes, at de fremstillede ionomere udviser fleksi-25 bilitet og høj oxygenpermeabilitet, men ikke lavtemperatur--fleksibilitet.The document mentions a large number of acrylates, e.g. isobutyl acrylate, as well as methacrylates, maleate and fumarates. Furthermore, it is mentioned that the prepared ionomers exhibit flexibility and high oxygen permeability, but not low temperature flexibility.

Ifølge den foreliggende opfindelse tilvejebringes en ionisk copolymer af ethylen, umættet carboxylsyre og mindst én blødgørende comonomer, hvilken ionisk copolymer har gode 30 lavtemperaturegenskaber, og er ejendommelig ved, at den umættede carboxylsyre er valgt blandt acrylsyre, methacryl-syre, maleinsyre, fumarsyre, itaconsyre og halvestere af maleinsyre, fumarsyre og itaconsyre, og at den blødgørende comonomer er valgt blandt n-propylacrylat, n-butylacrylat,According to the present invention there is provided an ionic copolymer of ethylene, unsaturated carboxylic acid and at least one softening comonomer, which ionic copolymer has good low temperature properties and is characterized in that the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, fumaric acid, and semesters of maleic acid, fumaric acid and itaconic acid and the softening comonomer is selected from n-propyl acrylate, n-butyl acrylate,

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2 2 -ethylhexylacryl at og 2 -methoxyethyl a cry 1 at, hvilken copolymer indeholder fra 10 til 87 vægt-% ethylen, fra 3 til 30 vægt-% umættet syre og fra 10 til 60 vægt-% blødgørende comonomer, copolymeren har fra 3 til 90% af carboxylsyre-5 grupperne ioniseret ved neutralisation med metalion valgt blandt natrium, kalium, zink, calcium, magnesium, lithium, aluminium, nikkel og chrom, og copolymeren er karakteriseret ved en lav grad af kædeforgrening på op til 2,8 kædeforgreninger pr. 1000 skelet-methylenenheder.2 2 -ethylhexylacrylic at and 2-methoxyethyl acrylic at which copolymer contains from 10 to 87% by weight of ethylene, from 3 to 30% by weight of unsaturated acid and from 10 to 60% by weight of softening comonomer, the copolymer has from 3 to 90% of the carboxylic acid groups ionized by neutralization with metal ion selected from sodium, potassium, zinc, calcium, magnesium, lithium, aluminum, nickel and chromium, and the copolymer is characterized by a low degree of chain branching of up to 2.8 chain branches per. 1000 skeletal methylene units.

10 Endvidere tilvejebringes der ifølge opfindelsen en fremgangsmåde til fremstilling af en ionisk copolymer med gode lavtemperaturegenskaber ifølge opfindelsen, hvor fremgangsmåden er valgt blandt direkte copolymerisation og pode-copolymerisation, hvorved 15 (A) den direkte copolymerisation omfatter polymerisering af ethylen, umættet carboxylsyre og mindst én comonomer i nærværelse af fri-radikal-polymerisationsinitiator ved forhøjet temperatur efterfulgt af neutralisation af carboxyl syregrupperne i den fremkomne direkte copolymer med 20 metalioner, og (B) podecopolymerisationen omfatter polymerisering af ethylen og mindst én comonomer i nærværelse af fri-radikal--polymerisationsinitiator ved forhøjet temperatur og podning af umættet carboxylsyre eller anhydrid på ethylen/-25 comonomer-polymerskelettet efterfulgt af neutralisation af carboxylsyregrupperne i den fremkomne podecopolymer med metalioner, og fremgangsmåden er ejendommelig ved, at der som blødgørende comonomer anvendes n-propylacrylat, n-butylacrylat, 2-ethyl-30 hexylacrylat og 2-methoxyethylacrylat, at der som den umættede syre anvendes en syre valgt blandt acrylsyre, methacryl-syre, maleinsyre, fumarsyre, itaconsyre og halvestere af maleinsyre, fumarsyre og itaconsyre, hvilken copolymer indeholder fra 10 til 87 vægt-% ethylen, fra 3 til 30 vægt-% 35 syre og fra 10 til 60 vægt-% blødgørende comonomer, idetFurther, according to the invention, there is provided a process for preparing an ionic copolymer of good low temperature properties according to the invention, the method being selected from direct copolymerization and graft copolymerization, wherein (A) the direct copolymerization comprises polymerization of ethylene, unsaturated carboxylic acid and at least one comonomers in the presence of free radical polymerization initiator at elevated temperature followed by neutralization of the carboxylic acid groups in the resulting direct copolymer with 20 metal ions, and (B) the graft copolymerization comprises polymerization of ethylene and at least one comonomer in the presence of free radical polymerization initiator by elevated temperature and grafting of unsaturated carboxylic acid or anhydride on the ethylene / -25 comonomer polymer backbone followed by neutralization of the carboxylic acid groups in the resulting graft copolymer with metal ions, and the process is characterized by the fact that as a softening comon n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are used, as the unsaturated acid, an acid selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and semesters of maleic acid, fumaric acid and itaconic acid, which contains from 10 to 87% by weight ethylene, from 3 to 30% by weight 35 acid and from 10 to 60% by weight softening comonomer,

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3 der anvendes en polymerisationstemperatur fra 100 til 200°C, og hvorved 3 til 90% af carboxylgrupperne i copolymeren neutraliseres med metalioner valgt blandt natrium, kalium, zink, calcium, magnesium, lithium, aluminium, nikkel og 5 chrom.3, a polymerization temperature of 100 to 200 ° C is used, whereby 3 to 90% of the carboxyl groups in the copolymer are neutralized with metal ions selected from sodium, potassium, zinc, calcium, magnesium, lithium, aluminum, nickel and 5 chromium.

Det har overraskende vist sig, at disse ionomere afledt af ethylen, en blødgørende comonomer og methacrylsyre har gode lavtemperaturegenskaber. Disse copolymere fremstillet ved lave reaktortemperaturer, der har en nedsat grad af 10 kædeforgrening og indeholder en passende blødgørende comonomer, giver ionomere, der ikke bliver så stive ved lave temperaturer og har en betydeligt forbedret bøjningsrevne-bestandighed (Ross Flex-værdi) i sammenligning med ionomere fremstillet ved højere reaktortemperaturer og indeholdende 15 blødgørende comonomere, som ikke giver homopolymere med lav glasovergangstemperatur.Surprisingly, these ionomers derived from ethylene, a softening comonomer and methacrylic acid have been found to have good low temperature properties. These copolymers prepared at low reactor temperatures, having a reduced chain 10 degree branching and containing an appropriate softening comonomer, provide ionomers that do not become as rigid at low temperatures and have a significantly improved bending crack resistance (Ross Flex value) compared to ionomers prepared at higher reactor temperatures and containing 15 softening comonomers which do not yield low glass transition temperature homopolymers.

I modsætning til teknikken kendt fra det ovennævnte DE offentliggørelsesskrift nr. 2.341.462 foretages der ifølge opfindelsen en omhyggelig udvælgelse af normale acrylater 20 (altså ikke isoacrylater, methacrylater, fumarater eller maleater) og en udvælgelse af et egnet temperaturområde ved polymerisationen på 100-200°C (men ikke højere), fortrinsvis under 160°C. Kernepunktet i opfindelsen er, at for at opnå lavtemperatur-fleksibilitet og sejhed skal der foretages en 25 udvælgelse i to henseender, både et valg af n-acrylater og et valg af lave polymerisationstemperaturer. Ét af disse valg er ikke tilstrækkeligt. Eksempelvis vil isobutylacrylat ikke være egnet, og en polymerisationstemperatur på 215°C vil heller ikke være egnet, heller ikke ved anvendelse af 30 n-butylacrylat.Contrary to the technique known from the aforementioned DE Publication No. 2,341,462, the invention makes a careful selection of normal acrylates 20 (i.e., isoacrylates, methacrylates, fumarates or maleate) and a selection of a suitable temperature range of 100-200 polymerization. ° C (but not higher), preferably below 160 ° C. The core point of the invention is that in order to achieve low temperature flexibility and toughness, a selection in two respects must be made, both a choice of n-acrylates and a choice of low polymerization temperatures. One of these choices is not enough. For example, isobutyl acrylate will not be suitable and a polymerization temperature of 215 ° C will also not be suitable, even using 30 n-butyl acrylate.

Ionomerene er følgelig anvendelig til sprøjtestøbte genstande, såsom skistøvler og skøjtestøvler, og som overtræk til stoffer.Accordingly, the ionomers are useful for injection molded articles, such as ski boots and skate boots, and as coatings for fabrics.

Da de ioniske copolymere ifølge opfindelsen har over-35 legne lavtempera tur egenskaber og lavere hårdhed end kommercielt tilgængelige ionomere, kan de desuden fungere somIn addition, since the ionic copolymers of the invention have superior low temperature properties and lower hardness than commercially available ionomers, they can act as

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4 erstatning for balata (balata er trans-l,4-polyisopren) i golfkugle-kapper. I overensstemmelse hermed vil golfkugler omfattende en kerne og en kappe, hvor kappen omfatter den ioniske copolymer ifølge opfindelsen, have et lignende 5 "smæld" og en lignende følelse som en golfkugle fremstillet med en balata-kappe. Ionomerene ifølge den foreliggende opfindelse kan også anvendes som modificerende midler til andre termoplastiske materialer, hvor de fungerer meget effektivt som sejhedsgivende midler.4 substitute for balata (balata is trans-1,4-polyisoprene) in golf ball jackets. Accordingly, golf balls comprising a core and a sheath, wherein the sheath comprises the ionic copolymer of the invention, will have a similar "melt" and a similar feel to a golf ball made with a balata sheath. The iononomers of the present invention can also be used as modifiers for other thermoplastic materials where they function very effectively as toughening agents.

10 Opfindelsen angår også anvendelsen af en ionisk co polymer ifølge opfindelsen i en termoplastisk blanding med materiale valgt blandt nylon, polypropylen, propylen-ethylen--copolymer, lineært polyethylen og ethylen/umættet carboxyl-syre-copolymer.The invention also relates to the use of an ionic copolymer of the invention in a thermoplastic mixture with material selected from nylon, polypropylene, propylene-ethylene copolymer, linear polyethylene and ethylene / unsaturated carboxylic acid copolymer.

15 Opfindelsen angår endvidere anvendelsen af en ionisk copolymer ifølge opfindelsen som kappe på en golfkugle omfattende en kerne og en kappe.The invention further relates to the use of an ionic copolymer according to the invention as a sheath on a golf ball comprising a core and a sheath.

Polymeren ifølge opfindelsen er en copolymer af ethy-len, umættet carboxylsyre og mindst én blødgørede copolymer, 20 der er copolymeriserbar med ethylen og giver en homopolymer med lav glasovergangstemperatur, hvor copolymeren er delvis neutraliseret med en metalion.The polymer of the invention is a copolymer of ethylene, unsaturated carboxylic acid and at least one plasticized copolymer, which is copolymerizable with ethylene and yields a low glass transition temperature homopolymer wherein the copolymer is partially neutralized with a metal ion.

Den umættede syre er fortrinsvis methacrylsyre og acrylsyre.The unsaturated acid is preferably methacrylic acid and acrylic acid.

25 Den blødgørende comonomer er fortrinsvis n-butyl- acrylat.The softening comonomer is preferably n-butyl acrylate.

Copolymeren indeholder fortrinsvis fra 60 til 75 vægt-% ethylen, fra 5 til 15 vægt-% umættet carboxylsyre og fra 10 til 30 vægt-%, især 15 til 25 vægt-%, blødgørende 30 comonomer.The copolymer preferably contains from 60 to 75% by weight of ethylene, from 5 to 15% by weight of unsaturated carboxylic acid, and from 10 to 30% by weight, especially 15 to 25% by weight, softening 30 comonomers.

Copolymeren ifølge den foreliggende opfindelse har fortrinsvis fra 35 til 75% af carboxylsyregrupperne ioniseret ved neutralisation med metalion valgt blandt natrium, kalium, zink, calcium og magnesium.Preferably, the copolymer of the present invention has ionized from 35 to 75% of the carboxylic acid groups by neutralization with metal ion selected from sodium, potassium, zinc, calcium and magnesium.

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55

De ioniske copolymere ifølge opfindelsen kan fremstilles ved direkte copolymerisation eller ved podecopolymerisa-tion. Den direkte polymerisationsproces omfatter polymerise-ring af ethylen, umættet carboxylsyre og blødgørende co-5 monomer i nærværelse af en fri-radikal-polymerisationsinitiator ved forhøjede temperaturer på fra 100 til 200°C, fortrinsvis fra 130 til 145°c ved tryk fra 140 til .350 mPa, efterfulgt af neutralisation af carboxylsyregrupperne i den fremstillede direkte copolymer med metalioner. En egnet 10 polymerisationsproces er beskrevet detaljeret i US-patent-skrift nr. 3.264.272 (bortset fra de uventede fordele, der opnås ved at anvende de lavest mulige reaktortemperaturer).The ionic copolymers of the invention can be prepared by direct copolymerization or by graft copolymerization. The direct polymerization process comprises polymerization of ethylene, unsaturated carboxylic acid and softening co-monomer in the presence of a free radical polymerization initiator at elevated temperatures of from 100 to 200 ° C, preferably from 130 to 145 ° C at pressures from 140 to .350 mPa, followed by neutralization of the carboxylic acid groups in the produced direct copolymer with metal ions. A suitable polymerization process is described in detail in U.S. Patent No. 3,264,272 (other than the unexpected benefits obtained by using the lowest possible reactor temperatures).

Podecopolymerisationsprocessen kan gennemføres ved at polymerisere ethylen og blødgørende copolymer i nærværelse 15 af fri-radikal-polymerisationsinitiator ved forhøjede temperaturer på fra 100 til 200°C, fortrinsvis fra 140 til 160°C, ved tryk fra 140 mPa til 350 mPa, og pode umættet carboxylsyre eller anhydrid på ethylen/blødgørende comonomer--polymer-skelettet og derefter neutralisere carboxylsyre-20 grupperne i den fremkomne podecopolymer med metalioner.The seed copolymerization process can be carried out by polymerizing ethylene and plasticizer copolymer in the presence of free radical polymerization initiator at elevated temperatures of from 100 to 200 ° C, preferably from 140 to 160 ° C, at pressures from 140 mPa to 350 mPa, and graft unsaturated. carboxylic acid or anhydride on ethylene / plasticizer comonomer - the polymer backbone and then neutralize the carboxylic acid groups in the resulting graft copolymer with metal ions.

Ionomerene ifølge den foreliggende opfindelse kan blandes med materiale valgt blandt nylon, polypropylen, propylen-ethylen-copolymere, lineært polyethylen og ethylen/-umættet carboxylsyre-copolymere. Disse blandinger vil gene-25 relt finde anvendelse som seje termoplaster.The ionomers of the present invention can be mixed with material selected from nylon, polypropylene, propylene-ethylene copolymers, linear polyethylene and ethylene / unsaturated carboxylic acid copolymers. These mixtures will generally find use as cool thermoplastics.

Ionomerene ifølge opfindelsen, der indeholder de ovenfor anførte monomere og er fremstillet ved de o-venfor anførte lave reaktionstemperaturer, er karakteriseret ved en lav grad af kædeforgrening, nemlig op til 30 ca. 2,8 kædeforgreninger pr. 1000 skelet-methylenenheder som bestemt ved C-13-NMR.The iononomers of the invention, which contain the above-mentioned monomers and are prepared at the low reaction temperatures mentioned above, are characterized by a low degree of chain branching, namely up to about 30%. 2.8 chain branches per 1000 skeletal methylene units as determined by C-13 NMR.

oisland

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66

Opfindelsen illustreres ved de følgende eksempler. Alle dele, procent og forhold er på vægtbasis, hvor der ikke er angivet andet.The invention is illustrated by the following examples. All parts, percentages and ratios are by weight, unless otherwise stated.

5 Sammenligningseksempel 1 og eksempel 1Comparative Example 1 and Example 1

Polymeren ifølge sammenligningseksempel 1, der indeholder n-butylacrylat, ethylen og methacrylsyre, fremstilles ved fri-radikal-polymerisation ved en reaktortemperatur på 220°C og 190 mPa. Monomertilsætningen ind-10 stilles således, at der fås en polymer indeholdende 10,1% methacrylsyre (MAA), 17%.n-butylacrylat (nBA) og 72,9% ethylen.The polymer of Comparative Example 1 containing n-butyl acrylate, ethylene and methacrylic acid is prepared by free radical polymerization at a reactor temperature of 220 ° C and 190 mPa. The monomer addition is adjusted so as to obtain a polymer containing 10.1% methacrylic acid (MAA), 17% n-butyl acrylate (nBA) and 72.9% ethylene.

Polymeren (basisharpiksen) omdannes til en na-triumionomer ved omsætning med et koncentrat indeholdende 15 natriumcarbonat. Således omsættes 1000 g af copolymeren med 72 g af et koncentrat (indeholdende 50% ^2002,^0 i en ethylen/methacrylsyre-copolymer indeholdende 11% MAA og maden smelteflydning på 100 g/10 min.). Reaktionen gennemføres i en dobbeltsnekkeekstruder under anvendelse af føl-20 gende betingelser:The polymer (base resin) is converted to a sodium ionomer by reaction with a concentrate containing sodium carbonate. Thus, 1000 g of the copolymer is reacted with 72 g of a concentrate (containing 50% 2002 2002, 0 0 in an ethylene / methacrylic acid copolymer containing 11% MAA and the food melt flow of 100 g / 10 min). The reaction is carried out in a twin screw extruder using the following conditions:

EXTRUDERINGSBETINGELSEREXTRUDERINGSBETINGELSER

Snekkehas- Temperatur, °C, zone Mængde Vakuum Vandtil-25 tighed førsel o/m__1_ 2 3 4 5 kg/time mm Hg cm^/time 50 135 236 247 262 280 2,27 762 20Wormhole Temperature, ° C, Zone Amount Vacuum Water Supply Flow o / m__1_ 2 3 4 5 kg / hr mm Hg cm ^ / hr 50 135 236 247 262 280 2.27 762 20

Polymeren ifølge eksempel 1 syntetiseres ved 30 140°C og 190 mPa. ComonomértiIsætningen indstilles såle des, at der fås en sammensætning, der ligner sammensætningen af polymeren ifølge sammenligningseksempel 1.The polymer of Example 1 is synthesized at 140 ° C and 190 mPa. The comonomer composition is adjusted so as to obtain a composition similar to the composition of the polymer of Comparative Example 1.

Polymeren omdannes til ionomer ved anvendelse af en ekstruderingsprocedure, der ligner den, der anven-35 des i sammenligningseksempel 1. I dette tilfælde bliver 2,27 kg polymer imidlertid blandet med 147 g af et zink- 0The polymer is converted to ionomer using an extrusion procedure similar to that used in Comparative Example 1. In this case, however, 2.27 kg of polymer is mixed with 147 g of a zinc oxide.

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7 oxidkoncentrat (30% ZnO, 1,5% zinkacetat i E/10 MAA-co-polymer). Sammenligning af resultaterne for polymerene ifølge sammenligningseksempel 1 og eksempel 1 viser, at polymeren fremstillet ved 220°C har en højere forøgelse 5 af bøjemodulus ved lavere temperaturer og en meget ringere bøjningsrevnebestandighed (Ross Flex-værdi) ved -20°C. Sammensætninger og egenskaber er sammenfattet i tabel I.7 oxide concentrate (30% ZnO, 1.5% zinc acetate in E / 10 MAA copolymer). Comparison of the results for the polymers of Comparative Example 1 and Example 1 shows that the polymer prepared at 220 ° C has a higher bending modulus 5 increase at lower temperatures and a much poorer bending crack resistance (Ross Flex value) at -20 ° C. Compositions and properties are summarized in Table I.

Der gennemføres også C-13-NMR-analyse på ethy-10 len/n-butylacrylat/methacrylsyre-copolymerene ifølge sammenligningseksempel 1 og eksempel 1 før deres omdannelse til ionomere. De opnåede resultater viser, at anvendelse af lave reaktortemperaturer (140°C) har næsten halveret antallet af alkylforgreninger pr. 1000 skelet-methylen-15 enheder i sammenligning med en copolymer fremstillet ved en høj reaktortemperatur på 220°C (jf. kædeforgreningstabellen nedenfor).C-13 NMR analysis is also performed on the ethyl / n-butyl acrylate / methacrylic acid copolymers of Comparative Example 1 and Example 1 prior to their conversion to ionomers. The results obtained show that the use of low reactor temperatures (140 ° C) has almost halved the number of alkyl branches per liter. 1000 skeletal methylene-15 units compared to a copolymer prepared at a high reactor temperature of 220 ° C (see the chain branch table below).

KÆDEFORGRENINGS-TABELTABLE-KÆDEFORGRENINGS

2 °

Antal butyl- eller større alkyl-forgre- MAA nBA Reaktor-temp. ninger pr. 1000 skelet-Eksempel % % °C_ -methylenenheder._ C-l 10,1 17,0 220 4,6 25 1 8,5 17,0 140 2,5 30 35Number of butyl or larger alkyl branch MAA nBA Reactor temp. per minute. 1000 skeleton Example%% ° C-methylene units. C-l 10.1 17.0 220 4.6 25 1 8.5 17.0 140 2.5 30 35

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9 DK 167025 B9 DK 167025 B

oisland

Eksempel 2 og 3.Examples 2 and 3.

Polymeren ifølge eksempel 2 fremstilles ved 190 mPa og 195°C og med sammensætningen 8,6% MAA, 24% nBA og 67,4% ethylen. Denne polymer omdannes derefter til 5 en zinkionomer ved omsætning med zinkacetat på en tovalset mølle. Således omsættes 100 g polymer med 6,6 g Zn(OAc) 2/2H20 i 25 cm^ vand ved 200°C. Den færdige iono-mer har en MI-værdi på 2,8.The polymer of Example 2 is prepared at 190 mPa and 195 ° C and with the composition 8.6% MAA, 24% nBA and 67.4% ethylene. This polymer is then converted to a zinc ionomer by reaction with zinc acetate on a two-roll mill. Thus, 100 g of polymer is reacted with 6.6 g of Zn (OAc) 2 / 2H 2 O in 25 cm 2 of water at 200 ° C. The finished ionomer has an MI value of 2.8.

Polymeren ifølge eksempel 3 fremstilles på 10 lignende måde som i sammenligningseksempel 1 og eksempel 1 og 2. Dog gennemføres omsætningen ved 140°C, og det forsøges at opnå en sammensætning som i eksempel 2. Således fremstilles en polymer indeholdende 9,4% MAA, 22,4% nBA og 68,2% ethylen og omdannes til ionomer.The polymer of Example 3 is prepared in a similar manner to that of Comparative Examples 1 and Examples 1 and 2. However, the reaction is carried out at 140 ° C and an attempt is made to obtain a composition as in Example 2. Thus, a polymer containing 9.4% MAA is prepared. 22.4% nBA and 68.2% ethylene and converted to ionomer.

15 Omdannelsen til ionomer opnås ved omsætning af 3 1 kg polymer med 60 g Zn(OAc) ^21^0 opløst i 150 cm vand på en 15 cm's tovalset mølle ved 190-200°C. Den fremkomne ionomer formes, og de fysiske egenskaber undersøges.The conversion to ionomer is achieved by reacting 3 1 kg of polymer with 60 g of Zn (OAc) ^ 21 ° D dissolved in 150 cm of water on a 15 cm bipolar mill at 190-200 ° C. The resulting ionomer is formed and the physical properties investigated.

Resultaterne af undersøgelsen af ionomeren iføl-20 ge eksempel 3 viser, at den har en lavere bøjemodulus end ionomeren ifølge eksempel 2 og har en betydelig bedre Ross Flex-holdbarhed ved -20°C. Sammensætninger og egenskaber er sammenfattet i tabel I.The results of the study of the ionomer of Example 3 show that it has a lower bending modulus than the ionomer of Example 2 and has a significantly better Ross Flex durability at -20 ° C. Compositions and properties are summarized in Table I.

25 Sammenligningseksempel 2 og 3.Comparative Examples 2 and 3.

Disse polymere fremstilles ved 140°C og 190 mPa og indeholder 70,3% ethylen, 19,8% isobutylacrylat (iBA) og 9,9% methacrylsyre og omdannes til ionomere. Bøjemodulus og Ross Flex-værdi for disse ionomere viser, at n-30 -butylacrylat-polymere er overlegne i forhold til isobut-ylacrylat-polymere. Homopolymere af iBA har en relativt høj glasovergangstemperatur. Sammensætninger og egenskaber er sammenfattet i tabel I.These polymers are prepared at 140 ° C and 190 mPa and contain 70.3% ethylene, 19.8% isobutyl acrylate (iBA) and 9.9% methacrylic acid and are converted to ionomers. Bending modulus and Ross Flex value for these ionomers show that n-30-butyl acrylate polymers are superior to isobutyl yl acrylate polymers. Homopolymers of iBA have a relatively high glass transition temperature. Compositions and properties are summarized in Table I.

Sammenligningseksempel 2-3 viser også, at der 35 er ringe eller ingen forskel mellem natrium- og zink-iono-mere. Den forbedrede bøjningsrevnebestandighed og den o 10Comparative Examples 2-3 also show that there is little or no difference between sodium and zinc ionizers. The improved bending crack resistance and the o 10

DK 167025 BDK 167025 B

reducerede lavtemperatur-stivhed skal således ikke tilskrives iontypen, men den blødgørende comonomer og graden af kædeforgrening.Thus, reduced low-temperature stiffness is not to be attributed to the ion type, but the softening comonomer and the degree of chain branching.

5 Eksempel 4Example 4

En blanding af polyamid-66 ("ZytellOl", E.I. du Pont de Nemours and Company) fremstilles indeholdende 30% af en zinkionomer fremstillet ved neutralisation af en copolymer med følgende sammensætning: E/28,0 nBA/10,1 10 MAA. Smelteblandingen produceres på en dobbeltsnekkeekst- ruder, idet der anvendes en snekkeform, der giver høj forskydning, og en smeltetemperatur på 270°C. Den fremkomne polymerblanding sprøjtestøbes til trækprøve- og bøjemo-dulusprøvestænger, idet der anvendes standard-polyamid-15 -formningsbetingelser. Resultaterne af undersøgelsen af fysiske egenskaber af disse formede prøvestykker er sammenfattet nedenfor:A mixture of polyamide-66 ("ZytellOl", E.I. du Pont de Nemours and Company) is prepared containing 30% of a zinc ionomer prepared by neutralizing a copolymer of the following composition: E / 28.0 nBA / 10.1 MAA. The melt mixture is produced on a double screw extruder, using a high shear screw mold and a melting temperature of 270 ° C. The resulting polymer blend is injection molded for tensile and bending modulus test rods using standard polyamide-15 molding conditions. The results of the physical properties study of these shaped specimens are summarized below:

Brud-trækstyrke^ 47 mPaBreakage tensile strength ^ 47 mPa

Forlængelse^ 110% 20 Bøjemodulus i tør til- 1500 mPa stand som formet (2)Extension ^ 110% 20 Bending modulus in dry to 1500 mPa state as shaped (2)

Izod-kærvslagstyrke ved 23°C 14 00 J/m.Izod jaw impact strength at 23 ° C 14 00 J / m.

ved -20°C 460 J/m.at -20 ° C 460 J / m.

25 Fodnoter: (1) Trækstyrke og procentisk forlængelse bestemmes ifølge ASTM-638.25 Footnotes: (1) Tensile strength and percent elongation are determined according to ASTM-638.

(2) Izod-kærvslagstyrke bestemmes ifølge ASTM-256.(2) Izod notch impact strength is determined according to ASTM-256.

I sammenligning med umodificeret polyamid-66 30 ("Zytel 101") viser resultaterne disse ionomeres evne til at gøre polyamid sejt i væsentlig grad og give en forbedret sejhed ved lave temperaturer.Compared to unmodified polyamide-66 ("Zytel 101"), the results demonstrate the ability of these ionomers to substantially make polyamide tough and provide improved toughness at low temperatures.

3535

Claims (15)

1. Ionisk copolymer af ethylen, umættet carboxylsyre og mindst én blødgørende comonomer, hvilken ionisk copolymer har gode lavtemperaturegenskaber, kendetegnet 5 ved, at den umættede carboxylsyre er valgt blandt acrylsyre, methacrylsyre, maleinsyre, fumarsyre, itaconsyre og halvestere af maleinsyre, fumarsyre og itaconsyre, og at den blødgørende comonomer er valgt blandt n-propylacrylat, n-butylacrylat, 2-ethylhexylacrylat og 2-methoxyethylacrylat, 10 hvilken copolymer indeholder fra 10 til 87 vægt-% ethylen, fra 3 til 30 vægt-% umættet syre og fra 10 til 60 vægt-% blødgørende comonomer, copolymeren har fra 3 til 90% af carboxylsyregrupperne ioniseret ved neutralisation med metalion valgt blandt natrium, kalium, zink, calcium, magnesium, 15 lithium, aluminium, nikkel og chrom, og copolymeren er karakteriseret ved en lav grad af kædeforgrening på op til 2,8 kædeforgreninger pr. 1000 skelet-methylenenheder.An ionic copolymer of ethylene, unsaturated carboxylic acid and at least one softening comonomer, which ionic copolymer has good low temperature properties, characterized in that the unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and half esters of maleic acid and half esters of maleic acid and that the softening comonomer is selected from n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate, which copolymer contains from 10 to 87 wt% ethylene, from 3 to 30 wt% unsaturated acid and from 10 to 60% by weight softening comonomer, the copolymer has ionized from 3 to 90% of the carboxylic acid groups by neutralization with metal ion selected from sodium, potassium, zinc, calcium, magnesium, lithium, aluminum, nickel and chromium, and the copolymer is characterized by a low degree of chain branch of up to 2.8 chain branches per 1000 skeletal methylene units. 2. Ionisk copolymer ifølge krav 1, kendetegnet ved, at den blødgørende comonomer er n-butylacrylat.Ionic copolymer according to claim 1, characterized in that the softening comonomer is n-butyl acrylate. 3. Ionisk copolymer ifølge krav 1,kendeteg ne t ved, at den er en direkte copolymer, og at den umættede syre er valgt blandt acrylsyre og methacrylsyre.3. Ionic copolymer according to claim 1, characterized in that it is a direct copolymer and that the unsaturated acid is selected from acrylic acid and methacrylic acid. 4. Ionisk copolymer ifølge krav 3, kendetegnet ved, at ethylen er til stede i en mængde på fra 60 25 til 75 vægt-%, den umættede syre er til stede i en mængde på fra 5 til 15 vægt-%, og den blødgørende comonomer er til stede i en mængde på fra 15 til 25 vægt-%.Ionic copolymer according to claim 3, characterized in that ethylene is present in an amount of from 60 to 75% by weight, the unsaturated acid is present in an amount of from 5 to 15% by weight, and the softening agent. comonomers are present in an amount of from 15 to 25% by weight. 5. Ionisk copolymer ifølge krav 4,kendetegne t ved, at den har fra 35 til 75% af carboxylsyregrup- 30 perae ioniseret ved neutralisation med metalion valgt blandt natrium, kalium, zink, calcium og magnesium.Ionic copolymer according to claim 4, characterized in that it has from 35 to 75% of carboxylic acid groups ionized by neutralization with metal ion selected from sodium, potassium, zinc, calcium and magnesium. 6. Ionisk copolymer ifølge krav 1, kendetegnet ved, at den er en podecopolymer.Ionic copolymer according to claim 1, characterized in that it is a graft copolymer. 7. Fremgangsmåde til fremstilling af en ionisk copoly-35 mer med gode lavtemperaturegenskaber ifølge krav l, hvor DK 167025 B fremgangsmåden er valgt blandt direkte copolymerisation og podecopolymerisation, hvorved (A) den direkte copolymerisation omfatter polymerisering af ethylen, umættet carboxylsyre og mindst én comonomer 5. nærværelse af fri-radikal-polymerisationsinitiator ved forhøjet temperatur efterfulgt af neutralisation af carboxylsyregrupperne i den fremkomne direkte copolymer med metalioner, og (B) podecopolymerisationen omfatter polymerisering af 10 ethylen og mindst én comonomer i nærværelse af fri-radi-kål-polymerisationsinitiator ved forhøjet temperatur og podning af umættet carboxylsyre eller anhydrid på ethylen/comonomer-polymerskelettet efterfulgt af neutralisation af carboxylsyregrupperne i den fremkomne pode-15 copolymer med metalioner, kendetegnet ved, at der som blødgørende comonomer anvendes n-propylacrylat, n-butylacrylat, 2-ethylhexylacrylat og 2-methoxyethylacrylat, at der som den umættede syre anvendes en syre valgt blandt acrylsyre, methacrylsyre, malein-20 syre, fumarsyre, itaconsyre og halvestere af maleinsyre, fumarsyre og itaconsyre, hvilken copolymer indeholder fra 10 til 87 vægt-% ethylen, fra 3 til 30 vægt-% syre og fra 10 til 60 vægt-% blødgørende comonomer, idet der anvendes en polymerisationstemperatur fra 100 til 200'C, og hvorved 25 3 til 90% af carboxylgrupperne i copolymeren neutraliseres med metalioner valgt blandt natrium, kalium, zink, calcium, magnesium, lithium, aluminium, nikkel og chrom.A process for preparing an ionic copolymer with good low temperature properties according to claim 1, wherein the DK 167025 B process is selected from direct copolymerization and graft copolymerization, wherein (A) the direct copolymerization comprises polymerization of ethylene, unsaturated carboxylic acid and at least one comonomer. 5. presence of free-radical polymerization initiator at elevated temperature followed by neutralization of the carboxylic acid groups in the resulting direct copolymer with metal ions, and (B) the graft copolymerization comprises polymerization of 10 ethylene and at least one comonomer in the presence of free-radical-polymerization initiator at elevated temperature and grafting of unsaturated carboxylic acid or anhydride on the ethylene / comonomer polymer backbone, followed by neutralization of the carboxylic acid groups in the resulting graft copolymer with metal ions, characterized in that n-propyl acrylate, n-butyl acrylate, 2-ethylacrylate, rylate and 2-methoxyethyl acrylate, that as the unsaturated acid is used an acid selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and semesters of maleic acid, fumaric acid and itaconic acid containing copolymer from 10 to 87% by weight of ethylene, from 3 to 30% by weight acid and from 10 to 60% by weight softening comonomer using a polymerization temperature of 100 to 200 ° C, whereby 25 to 90% of the carboxyl groups in the copolymer are neutralized with metal ions selected from sodium, potassium , zinc, calcium, magnesium, lithium, aluminum, nickel and chromium. 8. Fremgangsmåde ifølge krav 7, kendeteg-n e t ved, at der som blødgørende comonomer anvendes n- 3 0 -butylacrylat.Process according to claim 7, characterized in that n-30-butyl acrylate is used as a softening comonomer. 9. Fremgangsmåde ifølge krav 7, kendetegnet ved, at den gennemføres ved direkte copolymerisation, og den umættede syre vælges blandt acrylsyre og methacrylsyre.Process according to claim 7, characterized in that it is carried out by direct copolymerization and the unsaturated acid is selected from acrylic acid and methacrylic acid. 10. Fremgangsmåde ifølge krav 7-9, kendeteg net ved, at polymerisationstemperaturen er fra 130 til DK 167025 B 145°C, og at polymerisationstrykket er fra 140 til 350 mPa.Process according to claims 7-9, characterized in that the polymerization temperature is from 130 to DK 167025 B 145 ° C and that the polymerization pressure is from 140 to 350 mPa. 11. Fremgangsmåde ifølge krav 10, kendetegnet ved, at ethylenet er til stede i en mængde på fra 65 til 80 vægt-%, den umættede syre er til stede i en mængde 5 på fra 5 til 15 vægt-%, og den blødgørende comonomer er til stede i en mængde på fra 10 til 25 vægt-%.Process according to claim 10, characterized in that the ethylene is present in an amount of from 65 to 80% by weight, the unsaturated acid is present in an amount of 5 from 5 to 15% by weight, and the softening comonomer is present in an amount of from 10 to 25% by weight. 12. Fremgangsmåde ifølge krav 9, kendetegnet ved, at copolymeren har fra 35 til 75% af carboxyl-syregrupperne neutraliseret med metalion valgt blandt na- 10 trium, kalium, zink, calcium og magnesium.Process according to claim 9, characterized in that the copolymer has neutralized from 35 to 75% of the carboxylic acid groups with metal ion selected from sodium, potassium, zinc, calcium and magnesium. 13. Fremgangsmåde ifølge krav 7, kendetegnet ved, at den gennemføres ved podecopolymerisation.Process according to claim 7, characterized in that it is carried out by graft copolymerization. 14. Anvendelse af en ionisk copolymer ifølge krav 1, 4 eller 6 i en termoplastisk blanding med materiale valgt 15 blandt nylon, polypropylen, propylen-ethylen-copolymer, lineært polyethylen og ethylen/umættet carboxylsyre-copoly-mer.Use of an ionic copolymer according to claim 1, 4 or 6 in a thermoplastic mixture with material selected from nylon, polypropylene, propylene-ethylene copolymer, linear polyethylene and ethylene / unsaturated carboxylic acid copolymer. 15. Anvendelse af en ionisk copolymer ifølge krav l, 3, 5 eller 6 som kappe på en golf kugle omfattende en kerne 20 og en kappe.Use of an ionic copolymer according to claims 1, 3, 5 or 6 as a sheath on a golf ball comprising a core 20 and a sheath.
DK600283A 1982-12-28 1983-12-27 IONIC COPOLYMER WITH GOOD LOW TEMPERATURE CHARACTERISTICS, ITS MANUFACTURING AND USE DK167025C (en)

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